Decachlorobiphenyl and decabromobiphenyl have been analyzed under positive and negative ion chemical ionization and positive ion electron impact conditions for the purpose of using these compounds as references to evaluate the resolving power of mass spectrometers in a wide mass range (M/Z 100-1000). Molecular clusters and some fragments have been detected with different types of mass spectrometers: magnetic sector as well as quadrupoles, including A.E.I. MS-9, LKB-9000, LKB-2091, Finnigan 3200 and Finnigan 4000. The criteria to determine the resolving power have been found based on the measurement of the minima of two adjacent peaks of the molecular cluster of DCB or DBB. Molecular clusters for DCB and DBB were determined theoretically by plotting the individual ions which constitute each profile at the desired resolution using a standard Gaussian distribution of intensities, and then summing the individual ions with the weighting factors derived from the theoretical statistical isotope distribution ratios of carbon, chlorine, and bromine. By comparing the theoretical values of minima vs. resolution with the experimentally found values of minima between the same two adjacent peaks, the resolving power of a given mass spectrometer can be determined. The method